Neutralizing agents for resin emulsions

ABSTRACT

Incorporation of organic amines as neutralization agents in based phase inversion emulsification (PIE) processes to provide emulsification of high molecular amorphous and high molecular branch amorphous polyester resins, which are traditionally difficult to emulsify. The organic amines facilitate emulsification of these resins to achieve desired particle size with a narrow size distribution.

BACKGROUND

The present embodiments provide toners, and in particular, emulsionaggregation (EA) toners. These toners exhibit a low melt temperaturewhile simultaneously exhibiting excellent relative humidity sensitivityregarding charging properties. Also described are methods of making suchtoners.

Advantages of the toners described herein include, for example, theability to incorporate crystalline materials into the toner to achievelow melting characteristics without sacrificing relative humiditysensitivity.

Low melting, including ultra low melting, toners are known. For example,such toners may be comprised of an amorphous polyester material having acrystalline polyester material mixed therein. The crystalline polyestermaterial imparts the low melting temperature to the polyester toner. Anexample of such a low melting polyester toner is described in, forexample, U.S. Pat. No. 6,830,860 and U.S. Pat. Publication No.2008/0153027, the disclosures of which are incorporated herein byreference in their entirety.

Polyester toners have been prepared utilizing amorphous and crystallinepolyester resins. The incorporation of these polyester resins into tonerrequires that the resins first be formulated into emulsions prepared bysolvent containing batch processes, for example solvent-based phaseinversion emulsification (PIE) is known in the art. Ammonium hydroxide(NH₄OH) is known in the artas a “basic neutralization agent” in thepolyester emulsification process. See, e.g., U.S. Pat. No. 8,192,913.The ammonium hydroxide inverts the resin dissolved oil phase(resin/solvent solution) in water to form a stable aqueous emulsion.

In the PIE process, the type of base or neutralizing agent and ratio ofneutralizing agent to resin or solvent plays a very critical role. Thereare many input process parameters such as resin composition, resinmolecular weight and acid value that can vary which make it impossibleto emulsify high molecular weight branched amorphous polyester resins toproduce the desired particle size range (e.g., 100-250 nm) and a narrowparticle size distribution. Lot-to-lot variations of resin acid value,viscosity, and resin softening point requires adjustments in the PIEprocess parameters such as neutralization ratio and solvent ratio toachieve the desired toner particle size. Determining such adjustments istime-consuming and requires much trial and error to identify the exactconditions that will allow a resin lot to be successfully emulsified.Moreover, even with these modifications some polyester resins are notsuccessfully emulsified, with failed batches where particle size wasgreater than 400 nm. In particular, certain high molecular weightbranched amorphous polyester resins with lower acid values are notemulsified when ammonia hydroxide is used as the neutralization agent.

Therefore, there is a need to identify a new neutralization agent forthe preparation of polyester latexes suitable for polymers possessing avariation in parameters such as lower acid value, higher softening pointand the like.

SUMMARY

According to embodiments illustrated herein, there is provided a processcomprising mixing at least one polyester resin with a solvent to form aresin mixture; neutralizing the resin mixture with a neutralizing agentin water; and agitating the resin mixture and neutralizing agent inwater to form an aqueous emulsion, wherein the neutralizing agent is anorganic amine.

In particular, the present embodiments provide a process comprisingmixing at least one polyester resin with a solvent to form a resinmixture, wherein the polyester resin is a high molecular weightpolyester amorphous resin or a high molecular weight branched polyesteramorphous resin; neutralizing the resin mixture with a neutralizingagent in water; and agitating the resin mixture and neutralizing agentin water to form an aqueous emulsion, wherein the neutralizing agent isan organic amine selected from the group consisting of triethylamine,triethaneolamine, and mixtures thereof.

In embodiments, there is also provided an emulsion aggregate tonercomprising at least one polyester resin in a solvent; a neutralizingagent being an organic amine; and one or more toner additives.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the present embodiments, reference may bemade to the accompanying figures.

FIG. 1 is a graph illustrating a comparison of toner performance in Azone and J zone of toners produced by the present embodiments ascompared to those produced by a control; and

FIG. 2 is a graph illustrating a comparison of toner performance in Azone, which is an environment of 85% RH at 28° C., and J zone, which isan environment of 10% RH and 21° C., of toners with additives producedby the present embodiments as compared to those produced by a control.

FIG. 3 shows SEM micrographs illustrating the morphology texture andsurface texture of the toner particles according to the presentembodiments.

FIG. 4 shows SEM micrographs illustrating the morphology texture andsurface texture of the control toner particles.

FIG. 5 shows a graph illustration the gloss versus fusing temperature ofa control ink and inks prepared according to the present embodiments.

DETAILED DESCRIPTION

In the following description, it is understood that other embodimentsmay be utilized and structural and operational changes may be madewithout departure from the scope of the present embodiments disclosedherein.

One known method of forming emulsified polyester resin latex for use inpolyester emulsion aggregation toners is a solvent-based phase inversionemulsification (PIE) process. In this process, generally, ammoniumhydroxide is used as the neutralization agent to invert the resindissolved oil phase (resin/solvent solution) in water to form a stableaqueous emulsion. The present embodiments provide an organic amine, suchas triethylamine or triethaneolamine or other organic amines, as theneutralization agent. These neutralization agents may provide, incertain embodiments, easier emulsification of particular high molecularamorphous and high molecular weight branched amorphous polyester resinswhich possess very low acid value, high softening point or viscosity toachieve the desired toner particle size with narrow particle sizedistribution as a scalable emulsification process with a wide operatingwindow. These resulting polyester resin emulsions can be used in lowmelt or ultra low melt emulsion aggregation toners. In embodiments, theprocess of the present disclosure does not employ a basic neutralizationagent, such as, ammonium hydroxide.

In the present embodiments, the neutralization agent is an organicamine, such as, triethylamine, triethaneolamine, and mixtures thereof.

The organic amine neutralization agent can be used to emulsify apolyester resin to produce emulsions with particle size in the desiredrange of from about 100 nm to about 250 nm (in volume average diameter)with a narrow particle size distribution as measured by the CoulterCounter method. In further embodiments, the resulting emulsions have aparticle size in the desired range of from about 120 nm to about 220 nm,or from about 150 nm to about 200 nm with a narrow particle sizedistribution. The resulting polyester resin emulsions are useful inproducing low melt or ultra low melt emulsion aggregate toners.

The polyester resin that may be emulsified by the organic amineneutralization agent of the present disclosure includes any amorphouspolyester resin and/or crystalline polyester resin, especially thosewith a low acid value of from about 3 mg KOH/g of resin to about 200 mgKOH/g of resin, from about 5 mg KOH/g of resin to about 50 mg KOH/g ofresin, or from about 7 mg KOH/g of resin to about 15 mg KOH/g of resin.These polymer resins typically include acid terminated end groups.

The acid number may be detected by titration with KOH/methanol solutioncontaining phenolphthalein or bromothymol blue as the indicator. Theacid number may then be calculated based on the equivalent amount ofKOH/methanol required to neutralize all the acid groups on the resinidentified as the end point of the titration. In embodiments, thepolyester resin may include branched or straight chained amorphouspolyester. In embodiments, the polyester resin includes a high molecularweight polyester amorphous resin or a high molecular weight branchedpolyester amorphous resin.

Specific examples of amorphous polyester materials that may be usedinclude both branched and linear amorphous materials, and combinationsof branched and linear amorphous materials. The amorphous polyestermaterials may be formed by the polycondensation of an organic alcoholsuch as a diol or glycol and an acid, including anhydrides, optionallywith a multivalent polyacid or polyol as a branching agent, and apolycondensation catalyst. The amorphous polyesters may further becrosslinked, that is, may include crosslinked portions therein. Suitableacids may include, for example, succinic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid,isophthalic acid, terephthalic acid, hexachloroendo methylenetetrahydrophthalic acid, maleic acid, fumaric acid, chloromaleic acid,methacrylic acid, acrylic acid, itaconic acid, citraconic acid,mesaconic acid, maleic anhydride, phthalic anhydride, chlorendicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,endomethylene tetrahydrophthalic anhydride, tetrachlorophthalicanhydride, tetrabromophthalic anhydride, and the like and mixturesthereof. Suitable alcohols may include, for example, propylene glycol,ethylene glycol, diethylene glycol, neopentyl glycol, dipropyleneglycol, dibromoneopentyl glycol, propoxylated bisphenol A, ethoxylatedbisphenol A and other alkoxylated bisphenol A diols,2,2,4-trimethylpentane-1,3-diol, tetrabromo bisphenol dipropoxy ether,1,4-butanediol, and the like and mixtures thereof. Desirable amorphouspolyester materials may be prepared from diacids and/or anhydrides suchas, for example, maleic anhydride, fumaric acid, and the like andmixtures thereof, and diols such as, for example, propoxylated bisphenolA, propylene glycol, and the like and mixtures thereof. Apoly(propoxylated bisphenol A fumarate) polyester is suitable.

The amorphous polyester may also be comprised of an alkali sulfonatedpolyester resin, such as the metal or alkali salts ofcopoly(ethylene-terephthalate)-copoly(ethylene-5-sulfo-isophthalate),copoly(propylene-terephthalate)-copoly(propylene-5-sulfo-isophthalate),copoly(diethylene-terephthalate)-copoly(diethylene-5-sulfo-isophthalate),copoly(propylene-diethylene-terephthalate)-copoly(propylene-diethylene-5-sulfoisophthalate),copoly(propylene-butylene-terephthalate)-copoly(propylene-butylene-5-sulfo-isophthalate),copoly(propoxylated bisphenol-A-fumarate)-copoly(propoxylated bisphenolA-5-sulfo-isophthalate), copoly(ethoxylatedbisphenol-A-fumarate)-copoly(ethoxylatedbisphenol-A-5-sulfo-isophthalate), and copoly(ethoxylatedbisphenol-A-maleate)-copoly(ethoxylatedbisphenol-A-5-sulfo-isophthalate), wherein the alkali metal is, forexample, a sodium, lithium or potassium ion.

The amorphous polyester may include crosslinked portions therein, forexample such that the toner has a weight fraction of the microgel (a gelcontent) in the range of, for example, from about 0.001 to about 50weight percent, such as from about 0.1 to about 40 weight percent orfrom about 1 to about 10 weight percent, of the amorphous polyester. Thegel content may be achieved either by mixing in an amount of crosslinkedmaterial, or crosslinking portions of the amorphous polyester, forexample by including a crosslinking initiator in the amorphouspolyester. The initiators may be, for example, peroxides such as organicperoxides or azo-compounds, for example diacyl peroxides such asdecanoyl peroxide, lauroyl peroxide and benzoyl peroxide, ketoneperoxides such as cyclohexanone peroxide and methyl ethyl ketone, alkylperoxy esters such as t-butyl peroxy neodecanoate, 2,5-dimethyl2,5-di(2-ethyl hexanoyl peroxy)hexane, t-amyl peroxy 2-ethyl hexanoate,t-butyl peroxy 2-ethyl hexanoate, t-butyl peroxy acetate, t-amyl peroxyacetate, t-butyl peroxy benzoate, t-amyl peroxy benzoate, oo-t-butylo-isopropyl mono peroxy carbonate, 2,5-dimethyl 2,5-di(benzoylperoxy)hexane, oo-t-butyl o-(2-ethyl hexyl) mono peroxy carbonate, andoo-t-amyl o-(2-ethyl hexyl) mono peroxy carbonate, alkyl peroxides suchas dicumyl peroxide, 2,5-dimethyl 2,5-di(t-butyl peroxy)hexane, t-butylcumyl peroxide, bis(t-butyl peroxy)diisopropyl benzene, di-t-butylperoxide and 2,5-dimethyl 2,5-di(t-butyl peroxy)hexyne-3, alkylhydroperoxides such as 2,5-dihydro peroxy 2,5-dimethyl hexane, cumenehydroperoxide, t-butyl hydroperoxide and t-amyl hydroperoxide, and alkylperoxyketals such as n-butyl 4,4-di(t-butyl peroxy)valerate,1,1-di(t-butyl peroxy) 3,3,5-trimethyl cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amyl peroxy)cyclohexane, 2,2-di(t-butylperoxy)butane, ethyl 3,3-di(t-butyl peroxy)butyrate and ethyl3,3-di(t-amyl peroxy)butyrate, azobis-isobutyronitrile,2,2′-azobis(isobutyronitrile), 2,2′-azobis (2,4-dimethyl valeronitrile),2,2′-azobis(methyl butyronitrile), 1,1′-azobis(cyano cyclohexane),1,1-di(t-butyl peroxy)-3,3,5-trimethylcyclohexane, combinations thereofand the like. The amount of initiator used is proportional to the degreeof crosslinking, and thus the gel content of the polyester material. Theamount of initiator used may range from, for example, about 0.01 toabout 10 weight percent, such as from about 0.1 to about 5 weightpercent or the amorphous polyester. In the crosslinking, it is desirablethat substantially all of the initiator be used up. The crosslinking maybe carried out at high temperature, and thus the reaction may be veryfast, for example, less than 10 minutes, such as from about 20 secondsto about 2 minutes residence time.

Branching agents to generate a branched amorphous polyester may include,for example, a multivalent polyacid such as 1,2,4-benzenetricarboxylicacid, 1,2,4-cyclohexanetricarboxylic acid,2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylicacid, 1,2,5-hexanetricarboxylic acid,1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane,tetra(methylene-carboxyl)methane, and 1,2,7,8-octanetetracarboxylicacid, acid anhydrides thereof, and lower alkyl esters thereof havingfrom about 1 to about 6 carbon atoms; a multivalent polyol such assorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitane, pentaerythritol,dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol,1,2,5-pentatriol, glycerol, 2-methylpropanetriol,2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane,1,3,5-trihydroxymethylbenzene, mixtures thereof, and the like. Thebranching agent amount selected is, for example, from about 0.01 toabout 10 mole percent of the polyester material, such as from about 0.05to about 8 mole percent or from about 0.1 to about 5 mole percent of thepolyester material.

The amorphous polymer may comprise, for example, from about 50 to about95 percent by weight, such as from about 75 to about 95 percent byweight or from about 80 to about 90 percent by weight, of the binder. Inembodiments, the amorphous polymer material, such as the amorphouspolyester material, possesses, for example, a number average molecularweight (Mn), as measured by gel permeation chromatography (GPC), of fromabout 1,000 to about 500,000, such as from about 2,000 to about 250,000;a weight average molecular weight (Mw) of, for example, from about 1,000to about 600,000, such as from about 2,000 to about 300,000, asdetermined by GPC using polystyrene standards; and a molecular weightdistribution (Mw/Mn) of, for example, from about 1.5 to about 6, such asfrom about 2 to about 4.

In the present embodiments, the solvent-based phase inversionemulsification process generally involves the following steps:contacting a polyester resin with an organic solvent to form a resinmixture; neutralizing the resin mixture with a neutralizing agent (i.e.,organic amine) in the presence of water; agitating the resin mixturewith the neutralizing agent to form an aqueous emulsion. In embodiments,the process further includes adding water dropwise after the addition oforganic amine to the aqueous emulsion until phase inversion occurs toform a phase inversed mixture. The aqueous emulsion may be used to forman emulsion aggregate toner.

Any suitable organic solvent may be used to dissolve the polyester resinto form a resin mixture. Suitable organic solvents include, for example,alcohols, esters, ethers, ketones, amines, and combinations thereof.Specific examples of organic solvents include, for example, methanol,ethanol, propanol, isopropanol (IPA), butanol, ethyl acetate, methylethyl ketone, and the like, and combinations thereof. The organicsolvent may be present in an amount of, for example, from about 30% byweight to about 400% by weight of the resin, in embodiments, from about40% by weight to about 250% by weight of the resin, in embodiments, fromabout 50% by weight to about 100% by weight of the resin. Inembodiments, a solvent mixture can be used, which includes a mixture oftwo or more solvents. The ratio of any two organic solvents in a solventmixture may be from about 5:1 to about 50:1, from about 7:1 to about30:1, or from about 9:1 to about 25:1, or from about 3:1 to about 20:1.In embodiments, a solvent mixture comprises ketone and alcohol.

In embodiments, the organic solvent may be immiscible in water and mayhave a boiling point of from about 30° C. to about 120° C.

In embodiments, the resin dissolved oil phase comprises a weight ratioof the resin to solvent of about 2:1 to about 1:5 or of about 3:2 toabout 1:4 or of about 1:1 to about 1:2.

The resin mixture can be neutralized with the neutralizing agent of thepresent embodiments. An aqueous emulsion can be formed upon agitation ofthe resin mixture and the neutralizing agent in water. The aqueousemulsion can then be used to form an emulsion aggregate toner.

The neutralizing agent may be present in the aqueous emulsion in anamount of from about 0.001% by weight to 50% by weight of the resin, inembodiments from about 0.01% by weight to about 25% by weight of theresin, in embodiments from about 0.1% by weight to 5% by weight of theresin. In embodiments, the neutralizing agent may be added in the formof an aqueous solution. In other embodiments, the neutralizing agent maybe added in the form of a solid.

Utilizing the neutralization agent in combination with a resinpossessing acid groups, a neutralization ratio of from about 50% toabout 300% may be achieved, in embodiments from about 70% to about 200%.In embodiments, the neutralization ratio may be calculated as the molarratio of basic groups provided with the basic neutralizing agent to theacid groups present in the resin multiplied by 100%.

A low melt or ultra low melt toner typically has a glass transitiontemperature of from, for example, about 45° C. to about 85° C., such asfrom about 50° C. to about 65° C. or from about 50° C. to about 60° C.Such toners also exhibit a desirably low fixing or fusing temperature,for example a minimum fusing temperature of from about 75° C. to about150° C., such as from about 80° C. to about 150° C. or from about 90° C.to about 130° C. Such low melt characteristics are desirable in enablingthe toner to be fixed or fused onto an image receiving substrate such aspaper at a lower temperature, which can result in energy savings as wellas increased device speed.

In addition, the toner may have a relative humidity sensitivity of, forexample, from about 0.5 to about 10, such as from about 0.5 to about 5.Relative humidity (RH) sensitivity is a ratio of the charging of thetoner at high humidity conditions to charging at low humidityconditions. That is, the RH sensitivity is defined as the ratio of tonercharge in J-zone to toner charge in A-zone); thus, RH sensitivity isdetermined as (J-zone charge)/(A-zone charge). Ideally, the RHsensitivity of a toner is as close to 1 as possible, indicating that thetoner charging performance is the same in low and high humidityconditions, that is, that the toner charging performance is unaffectedby the relative humidity.

A toner having the above low melt/ultra low melt characteristics and RHsensitivity characteristics may be comprised of a binder comprising bothan amorphous polymer material, such as a resin or polymer, and acrystalline polymer material, such as a resin or binder.

The toner may desirably be a polyester toner, comprised of both anamorphous polyester material, such as a resin or polymer, and acrystalline polyester material, such as a resin or binder.

The binder also includes a crystalline polymer material. As used herein,“crystalline” refers to, for example, a material with a threedimensional order, and encompasses both crystalline and semicrystallinematerials. “Semicrystalline” refers to materials with a crystallinepercentage of less than 100%, for example, from about 10 to about 60%.The polymer is considered crystalline when it is comprised of crystalswith a regular arrangement of its atoms in a space lattice, and thusprovides a defined melting point. An amorphous polymer, on the otherhand, lacks such an organized crystalline structure and lacks a definedmelting point.

The crystalline polymer material may be of the same kind as or differentkind from the polymer of the amorphous polyester material. For example,both polymer materials may be of the same kind by both being polyestermaterials.

Any crystalline polymer material may be used, for example includingpolyesters, polyester-polyimides, polyimides, polyamides and the like.In certain embodiments, a crystalline polyester material is used.

Acid groups which may be present include carboxylic acid groups, and thelike. The crystalline polymer may have an acid number of from about fromabout 3 mg KOH/g of resin to about 200 mg KOH/g of resin, inembodiments, from about 5 mg KOH/g of resin to about 50 mg KOH/g ofresin, or from about 7 mg KOH/g of resin to about 15 mg KOH/g of resin.

A crystalline polyester may be prepared by polycondensation of anorganic alcohol such as diol or glycol and an organic diacid in thepresence of a polycondensation catalyst. Additionally, in place of anorganic diacid, an organic diester may also be selected, and where analcohol byproduct is generated.

For example, the crystalline polyester may be obtained by polycondensingan alcohol component comprising 80% by mole or more of an aliphatic diolhaving 2 to 6 carbon atoms, such as 4 to 6 carbon atoms, with acarboxylic acid component comprising 80% by mole or more of an aliphaticdicarboxylic acid compound having 2 to 8 carbon atoms, such as 4 to 6carbon atoms or 4 carbon atoms. See, for example, U.S. Pat. No.6,780,557. The aliphatic diol having 2 to 6 carbon atoms may includeethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol,1,4-butanediol, and the like. It is desirable that the aliphatic diol iscontained in the alcohol component in an amount of about 80% by mole ormore, such as from about 85 to 100% by mole. The alcohol component mayalso contain a polyhydric alcohol component other than the aliphaticdiol having 2 to 6 carbon atoms. Such a polyhydric alcohol componentincludes a divalent aromatic alcohol such as an alkylene (2 to 3 carbonatoms) oxide adduct (average number of moles added being 1 to 10) ofbisphenol A, such aspolyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane andpolyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane; a trihydric orhigher polyhydric alcohol component such as glycerol, pentaerythritoland trimethylolpropane; and the like. The aliphatic dicarboxylic acidcompound having 2 to 8 carbon atoms includes oxalic acid, malonic acid,maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconicacid, succinic acid, adipic acid, acid anhydrides thereof, alkyl (1 to 3carbon atoms) esters thereof, and the like. It is desirable that thealiphatic dicarboxylic acid compound is contained in the carboxylic acidcomponent in an amount of about 80% by mole or more, such as from about85 to 100% by mole. Among them, from the viewpoint of the storageability of the crystalline polyester, it is desirable that fumaric acidis contained in the carboxylic acid component in an amount of about 60%by mole or more, such as about 70 to 100% by mole. The carboxylic acidcomponent may contain a polycarboxylic acid component other than thealiphatic dicarboxylic acid compound having 2 to 8 carbon atoms. Such apolcarboxylic acid component includes aromatic dicarboxylic acids suchas phthalic acid, isophthalic acid and terephthalic acid; aliphaticdicarboxylic acids such as sebacic acid, azelaic acid, n-dodecylsuccinicacid and n-dodecenylsuccinic acid; alicyclic carboxylic acids such ascyclohexanedicarboxylic acid; tricarboxylic or higher polycarboxylicacids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid) andpyromellitic acid; acid anhydrides thereof, alkyl (1 to 3 carbon atoms)esters thereof, and the like.

The crystalline polyester may also be derived from monomers containingan alcohol component such as a diol and/or comprising a trihydric orhigher polyhydric alcohol, and an organic acid and/or a carboxylic acidcomponent comprising a tricarboxylic or higher polycarboxylic acidcompound as detailed in U.S. Pat. No. 6,653,435, incorporated herein byreference in its entirety. The trihydric or higher polyhydric alcoholsinclude sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol,dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol,1,2,5-pentanetriol, glycerol, 2-methylpropanetriol,2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane,1,3,5-trihydroxymethylbenzene, and the like. Examples of thetricarboxylic or higher polycarboxylic acid compound include1,2,4-benzenetricarboxylic acid (trimellitic acid),2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylicacid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid,1,3-dicarboxy-2-methyl-2-methylenecarboxypropane,1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane,1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimeracid, acid anhydrides thereof, alkyl (1 to 3 carbon atoms) estersthereof, and the like.

The aforementioned crystalline polyester materials may be prepared bythe polycondensation reactions described in the aforementioned patents.

In embodiments, the crystalline polyester material may be derived from amonomer system comprised of an alcohol selected from among1,4-butanediol, 1,6-hexanediol, and mixtures thereof with a dicarboxylicacid selected from among fumaric acid, succinic acid, oxalic acid,adipic acid, and mixtures thereof. For example, the crystallinepolyester may be derived from 1,4-butanediol and/or 1,6-hexanediol andfumaric acid, the polyester having a crystallinity of about 25 to about75% such as from about 40 to about 60%.

Examples of organic diols include aliphatic diols with from about 2 toabout 36 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanedioi,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol andthe like; alkali sulfo-aliphatic diols such as sodio2-sulfo-1,2-ethanediol, lithio 2-sulfo-1,2-ethanediol, potassio2-sulfo-1,2-ethanediol, sodio 2-sulfo-1,3-propanediol, lithio2-sulfo-1,3-propanediol, potassio 2-sulfo-1,3-propanediol, mixturethereof, and the like.

Examples of organic diacids or diesters selected for the preparation ofthe crystalline resins include oxalic acid, succinic acid, glutaricacid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalicacid, isophthaiic acid, terephthalic acid, naphthalene-2,6-dicarboxylicacid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid,malonic acid and mesaconic acid, a diester or anhydride thereof.

Generally, a stoichiometric equimolar ratio of organic diol and organicdiacid is utilized. However, in some instances, wherein the boilingpoint of the organic diol is from about 180° C. to about 230° C., anexcess amount of diol may be utilized and removed during thepolycondensation process.

Polycondensation catalyst examples for either the crystalline oramorphous polyesters include tetraalkyl titanates, dialkyltin oxide suchas dibutyltin oxide, tetraalkyltin such as dibutyltin dilaurate,dialkyltin oxide hydroxide such as butyltin oxide hydroxide, aluminumalkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, ormixtures thereof; and which catalysts are selected in amounts of, forexample, from about 0.01 mole percent to about 5 mole percent based onthe starting diacid or diester used to generate the polyester resin.

Additional examples of crystalline polymer materials include otherpolyesters, polyamides, polyimides, polyolefins, polyethylene,polybutylene, polyisobutyrate, ethylene-propylene copolymers,ethylene-vinyl acetate copolymers, polypropylene, mixtures thereof, andthe like. Specific examples include poly(ethylene-adipate),poly(propylene-adipate), poly(butylene-adipate),poly(pentylene-adipate), poly(hexylene-adipate), poly(octylene-adipate),poly(ethylene-succinate), poly(propylene-succinate),poly(butylene-succinate), poly(pentylene-succinate),poly(hexylene-succinate), poly(octylene-succinate),poly(ethylene-sebacate), poly(propylene-sebacate),poly(butylene-sebacate), poly(pentylene-sebacate),poly(hexylene-sebacate), poly(octylene-sebacate), alkalicopoly(5-sulfoisophthaloyl)-copoly(ethylene-adipate), alkalicopoly(5-sulfoisophthaloyl)-copoly(propylene-adipate), alkalicopoly(5-sulfoisophthaloyl)-copoly(butylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(octylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(ethylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly (propylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(butylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(octylene-adipate), alkalicopoly(5-sulfoisophthaloyl)-copoly(ethylene-succinate), alkalicopoly(5-sulfoisophthaloyl)-copoly(propylene-succinate), alkalicopoly(5-sulfoisophthaloyl)-copoly(butylenes-succinate), alkalicopoly(5-sulfoisophthaloyl)-copoly(pentylene-succinate), alkalicopoly(5-sulfoisophthaloyl)-copoly(hexylene-succinate), alkalicopoly(5-sulfoisophthaloyl)-copoly(octylene-succinate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(ethylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(propylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(butylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(octylene-sebacate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(ethylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(propylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(butylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkalicopoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate),poly(octylene-adipate), and wherein alkali is a metal like sodium,lithium or potassium. Examples of polyamides includepoly(ethylene-adipamide), poly(propylene-adipamide),poly(butylenes-adipamide), poly(pentylene-adipamide),poly(hexylene-adipamide), poly(octylene-adipamide),poly(ethylene-succinamide), and poly(propylene-sebecamide). Examples ofpolyimides include poly(ethylene-adipimide), poly(propylene-adipimide),poly(butylene-adipimide), poly(pentylene-adipimide),poly(hexylene-adipimide), poly(octylene-adipimide),poly(ethylene-succinimide), poly(propylene-succinimide), andpoly(butylene-succinimide),

The crystalline material in the toner may have a melting temperature of,for example, from about 30° C. to about 12° C., such as from about 50°C. to about 90° C., and a recrystallization temperature of at leastabout 40° C., such as a recrystallization temperature of, for example,from about 50° C. to about 65° C. In embodiments, the crystalline resinis a sulfonated polyester resin. The crystalline resin may be sulfonatedfrom about 0.5 weight percent to about 4.5 weight percent, such as fromabout 1.5 weight percent to about 4.0 weight percent, of the crystallinepolyester. The crystalline material may possess, for example, a numberaverage molecular weight (Mn), as measured by gel permeationchromatography (GPC) of, for example, from about 1,000 to about 250,000,and preferably from about 2,000 to about 50,000 and a weight averagemolecular weight (Mw) of, for example, from about 1,000 to about250,000, such as from about 2,000 to about 100,000, as determined by GPCusing polystyrene standards. The molecular weight distribution (Mw/Mn)of the crystalline material may be, for example, from about 2 to about6, and more specifically, from about 2 to about 4.

The crystalline polymer material is, for example, present in an amountof from about 5 to about 50 percent by weight of the binder, such asfrom about 5 to about 25 percent by weight or from about 10 to about 25%by weight, of the binder.

In addition to the binder, the toner may also include at least onecolorant and/or at least one wax. Colorant includes pigment, dye,mixtures of dyes, mixtures of pigments, mixtures of dyes and pigments,and the like.

When present, the colorant may be added in an effective amount of, forexample, from about 1 to about 25 percent by weight of the toner, suchas in an amount of from about 2 to about 12 weight percent of the toner.Suitable example colorants include, for example, carbon black like REGAL330® magnetites, such as Mobay magnetites MO8029™, MO8060™; Columbianmagnetites; MAPICO BLACKS™ and surface treated magnetites; Pfizermagnetites CB4799™, CB5300™, CB5600™, MCX6369™; Bayer magnetites,BAYFERROX 8600™, 8610™; Northern Pigments magnetites, NP-604™, NP-608™;Magnox magnetites TMB-100™, or TMB-104™; and the like. As coloredpigments, there may be selected cyan, magenta, yellow, red, green,brown, blue or mixtures thereof. Specific examples of pigments includephthalocyanine HELIOGEN BLUE L6900™, D6840™, D7080™, D7020™, PYLAM OILBLUE™ PYLAM OIL YELLOW™, PIGMENT BLUE 1™ available from Paul Uhlich &Company, Inc., PIGMENT VIOLET 1™, PIGMENT RED 48™, LEMON CHROME YELLOWDCC1026™, E.D. TOLUIDINE RED™ and BON RED C™ available from DominionColor Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL™,HOSTAPERM PINK E™ from Hoechst, and CINQUASIA MAGENTA™ available fromE.I. DuPont de Nemours & Company, and the like. Generally, colorantsthat can be selected are black, cyan, magenta, or yellow, and mixturesthereof. Examples of magentas are 2,9-dimethyl-substituted quinacridoneand anthraquinone dye identified in the Color Index as CI-60710, CIDispersed Red 15, diazo dye identified in the Color Index as CI-26050,CI Solvent Red 19, and the like, Illustrative examples of cyans includecopper tetra(octadecyl sulfonamido)phthalocyanine, x-copperphthalocyanine pigment listed in the Color Index as CI-74160, CI PigmentBlue, and Anthrathrene Blue, identified in the Color Index as CI-69810,Special Blue X-2137, and the like; while illustrative examples ofyellows are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, amonoazo pigment identified in the Color Index as CI-12700, CI SolventYellow 16, a nitrophenyl amine sulfonamide identified in the Color Indexas Foron Yellow SE/GLN, CI Dispersed Yellow 332,5-dimethoxy-4-sulfonanilide phenylazo-4′-chloro-2,5-dimethoxyacetoacetanilide, and Permanent Yellow FGL. Colored magnetites, such asmixtures of MAP ICO BLACK™, and cyan components may also be selected ascolorants. Other known colorants can be selected, such as Levanyl BlackA-SF (Miles, Bayer) and Sunsperse Carbon Black LHD 9303 (Sun Chemicals),and colored dyes such as Neopen Blue (BASF), Sudan Blue OS (BASF), PVFast Blue B2G01 (American Hoechst), Sunsperse Blue BHD 6000 (SunChemicals), Irgalite Blue BCA (Ciba-Geigy), Paliogen Blue 6470 (BASF),Sudan III (Matheson, Coleman, Bell), Sudan II (Matheson, Coleman, Bell),Sudan IV (Matheson, Coleman, Bell), Sudan Orange G (Aldrich), SudanOrange 220 (BASF), Paliogen Orange 3040 (BASF), Ortho Orange OR 2673(Paul Uhlich), Paliogen Yellow 152, 1560 (BASF), Lithol Fast Yellow0991K (BASF), Paliotol Yellow 1840 (BASF), Neopen Yellow (BASF),Novoperm Yellow FG 1 (Hoechst), Permanent Yellow YE 0305 (Paul Uhlich),Lumogen Yellow D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals),Suco-Gelb L1250 (BASF), Suco-Yellow D1355 (BASF), Hostaperm Pink E(American Hoechst), Fanal Pink D4830 (BASF), Cinquasia Magenta (DuPont),Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet forThermoplast NSD PS PA (Ugine Kuhlmann of Canada), E.D. Toluidine Red(Aldrich), Lithol Rubine Toner (Paul Uhlich), Lithol Scarlet 4440(BASF), Bon Red C (Dominion Color Company), Royal Brilliant Red RD-8192(Paul Uhlich), Oracet Pink RF (Ciba-Geigy), Paliogen Red 3871K (BASF),Paliogen Red 3340 (BASF), and Lithol Fast Scarlet L4300 (BASF).

Optionally, a wax may be present in an amount of from about 1 to about30% by weight of the toner, such as from about 1 to about 15% by weightof the toner. The wax may function as, for example, a release agent toassist in the release of toner images from a fuser roll. Examples ofwaxes are known, and include, for example, alkylenes, such aspolypropylene, polyethylene, and the like. The waxes may be hydrophobicand essentially water insoluble. The wax may include (1) natural waxessuch as those extracted from vegetables (carnauba wax, Japan wax,bayberry wax) or animals (beeswax, shellac wax, spermaceti wax); (2)mineral waxes, such as those extracted, for example, from bituminouslignite or share (montan wax, ozokerite wax, ceresin wax); (3) petroleumwaxes, complex mixtures of paraffinic hydrocarbons obtained from thedistillation of crude petroleum (paraffin wax), or by dewaxing heavylubricating oils and petrolatum residues (microcrystalline wax); and (4)synthetic waxes generated, for example, by chemical processes includingpetroleum, Fischer-Tropsch (by coal gasification), polyethylene,polypropylene, acrylate, fatty acid amides, silicone andpolytetrafluoroethylene waxes. Specific examples of waxes for use hereininclude polypropylenes and polyethylenes such as commercially availablefrom Allied Chemical and Petrolite Corporation (for example, thePOLYWAX™ line of waxes), wax emulsions available from Michaelman, Inc.and the Daniels Products Company, EPOLENE N-15™ commercially availablefrom Eastman Chemical Products, Inc., VISCOL 550-P™ a low weight averagemolecular weight polypropylene available from Sanyo Kasei K. K., andsimilar materials. Additional examples of suitable waxes include naturalwaxes such as carnauba wax, functionalized waxes such as amines, amides,for example AQUA SUPERSLIP 6550™, SUPERSLIP 6530™ available from MicroPowder Inc., fluorinated waxes, for example POLYFLUO 190™, POLYFLUO200™, POLYSILK 19™, POLYSILK 14™ available from Micro Powder Inc., mixedfluorinated, amide waxes, for example MICROSPERSION 19™ also availablefrom Micro is Powder Inc., imides, esters, quaternary amines, carboxylicacids or acrylic polymer emulsion, for example JONCRYL™ waxes, allavailable from SC Johnson Wax, chlorinated polypropylenes andpolyethylenes available from Allied Chemical and Petrolite Corporationand SC Johnson Wax, and the like. Mixtures of waxes may also be used.

The toners may also include any additional additives, such as chargeenhancing agents, embrittling agents, flow agents such as colloidalsilica, external surface additives such as silica and/or titania, andthe like, as desired or necessary.

The emulsion aggregation toner has advantages in achieving a small sizedtoner particle with a substantially uniform particle size distribution.For example, the toner particles may have an average particle size offrom about 3 to about 25 μm, such as from about 5 to about 15 μm or fromabout 5 to about 12 μm, as determined by use of a Coulter Counter orsimilar device. The volume average and number average geometric sizedistribution (GSDv and GSDn) of the toner particles of embodiments maybein a range of from about 1.1 to about 1.3, as measured with a suitableprocess such as Coulter Counter Multisizer II. The volume average andthe number average distribution, respectively, are determined based onthe particle diameters at which a cumulative percentage of particles areattained. In this regard, the particle diameters at which a cumulativepercentage of 16 percent are attained are defined as volume D16 percentand number D16 percent, respectively, and the particle diameters atwhich a cumulative percentage of 84 percent are attained are defined asvolume D84 percent and number D84 percent, respectively. Theseaforementioned volume average particle size distribution index GSDv andnumber average particle size distribution index GSDn can be expressed byusing D16 percent and D84 percent in cumulative distribution, whereinthe volume average particle size distribution index GSDv is expressed as(volume D84 percent/volume D16 percent)½ and the number average particlesize distribution index GSDn is expressed as (number D84 percent/numberD16 percent)½.

The toner may be made by melt mixing the ingredients together in amixing device. Examples of mixing devices are twin screw extruders,Banbury/rollmill, kneaders, and the like.

The toner particles may also be made by chemical processes such as byemulsion aggregation. Any suitable emulsion aggregation procedure may beused in forming the emulsion aggregation toner particles withoutrestriction. These procedures typically include the basic process stepsof at least aggregating an emulsion containing the binder components,one or more colorants, optionally one or more surfactants, optionallyone or more waxes, optionally a coagulant and one or more additionaloptional additives to form aggregates, subsequently coalescing theaggregates, and then recovering, optionally washing and optionallydrying the obtained emulsion aggregation toner particles.

An example emulsion aggregation procedure may comprise providing a latexor emulsion of the binder components, any wax, any colorant, and anyother desired or required additives. In embodiments, the amorphous andcrystalline polyesters may be formed in different emulsions and mixedtogether in a pre-toner mixture prior to aggregation. The pH of thepre-toner mixture may be adjusted to between about 4 to about 5. The pHof the pre-toner mixture may be adjusted by an acid such as, forexample, acetic acid, nitric acid or the like. Additionally, inembodiments, the pre-toner mixture optionally maybe homogenized bymixing at about 600 to about 4,000 revolutions per minute. The particlesmay then be aggregated, for example through addition of an aggregatingagent or coagulant to the emulsion. The aggregating agent is generallyan aqueous solution of a divalent cation or a multivalent cationmaterial. The aggregating agent may be, for example, polyaluminumhalides such as polyaluminum chloride (PAC), or the correspondingbromide, fluoride, or iodide, polyaluminum silicates such aspolyaluminum sulfosilicate (PASS), and water soluble metal saltsincluding aluminum chloride, aluminum nitrite, aluminum sulfate,potassium aluminum sulfate, calcium acetate, calcium chloride, calciumnitrite, calcium oxylate, calcium sulfate, magnesium acetate, magnesiumnitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate,zinc chloride, zinc bromide, magnesium bromide, copper chloride, coppersulfate, and combinations thereof. Aggregation may be accomplished attemperatures greater than about 60° C. Following aggregation to thedesired particle size, the aggregates may be coalesced. Coalescence maybe accomplished by heating the aggregate mixture to a temperature thatis about 5 to about 20° C. above the Tg of the binder. Generally, theaggregated mixture is heated to a temperature of about 50 to about 80°C. In embodiments, coalescence is accomplished by also stirring themixture at a temperature of from about 200 to about 750 revolutions perminute. Optionally, during coalescence, the particle size of the tonerparticles may be controlled and adjusted to a desired size by adjustingthe pH of the mixture. Generally, to control the particle size, the pHof the mixture is adjusted to between about 5 to about 7 using a basesuch as, for example, sodium hydroxide. After coalescence, the mixtureis cooled to room temperature. After cooling, the mixture of tonerparticles is washed with water and then dried. Drying may beaccomplished by any suitable method for drying including freeze drying.

The process may or may not include the use of surfactants. If used, thesurfactants may be anionic, cationic or nonionic. Anionic surfactantsinclude sodium dodecylsulfate (SDS), sodium dodecyl benzene sulfonate,sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates andsulfonates, abitic acid, and the NEOGEN brand of anionic surfactantsavailable from Daiichi Kogyo Seiyaku Co. Ltd. Examples of cationicsurfactants include dialkyl benzene alkyl ammonium chloride, lauryltrimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkylbenzyl dimethyl ammonium bromide, benzalkonium chloride, cetylpyridinium bromide, C12, C15, C17 trimethyl ammonium bromides, halidesalts of quaternized polyoxyethylalkylamines, dodecyl benzyl triethylammonium chloride, MIRAPOL and ALKAQUAT available from Alkaril ChemicalCompany, SANISOL (benzalkonium chloride), available from Kao Chemicals,and the like. Examples of nonionic surfactants include polyvinylalcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose,propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose,polyoxyethylene cetyl ether, polyoxyethylene lauryl ether,polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether,polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate,polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether,dialkylphenoxy poly(ethyleneoxy) ethanol, available from Rhone-PoulencInc. as IGEPAL CA-210, IGEPAL CA-520, IGEPAL CA-720, IGEPAL CO-890,IGEPAL CO-720, IGEPAL CO-290, IGEPAL CA-210, ANTAROX 890 and ANTAROX897.

Following formation of the toner particles, external additives may beadded to the toner particle surface by any suitable procedure such asthose well known in the art. For example, suitable surface additivesthat may be used are one or more of Si02, metal oxides such as, forexample, TiO2 and aluminum oxide, and a lubricating agent such as, forexample, a metal salt of a fatty acid (for example, zinc stearate(ZnSt), calcium stearate) or long chain alcohols such as UNILIN 700.Si02 and TiO2 may be surface treated with compounds including DTMS(dodecyltrimethoxysilane) or HMDS (hexamethyldisilazane). Examples ofthese additives are a silica coated with a mixture of HMDS andaminopropyltriethoxysilane; a silica coated with PDMS(polydimethylsiloxane); a silica coated withoctamethylcyclotetrasiloxane; a silica coated withdimethyldichlorosilane; DTMS silica, obtained from Cabot Corporation,comprised of a fumed silica, for example silicon dioxide core L90 coatedwith DTMS; silica coated with an amino functionalizedorganopolysiloxane; X24 sol-gel silica available from Shin-Etsu ChemicalCo., Ltd.; TS530 from Cabot Corporation, Cab-O-Sil Division, a treatedfumed silica; titania comprised of a crystalline titanium dioxide corecoated with DTMS. The titania may also be untreated, for example P-25from Nippon Aerosil Co., Ltd. Zinc stearate may also be used as anexternal additive, the zinc stearate providing lubricating properties.Zinc stearate provides developer conductivity and tribo enhancement,both due to its lubricating nature. In addition, zinc stearate canenable higher toner charge and charge stability by increasing the numberof contacts between toner and carrier particles. Calcium stearate andmagnesium stearate provide similar functions. Most preferred is acommercially available zinc stearate known as ZINC STEARATE L, obtainedfrom Ferro Corporation.

The toners are sufficient for use in an electrostatographic orxerographic process. In this regard, the toner particles may beformulated into a developer composition, optionally by mixing withcarrier particles. The toner concentration in each developer may rangefrom, for example, about 1 to about 25%, such as from about 2 to about15%, by weight of the total weight of the developer. Illustrativeexamples of carrier particles that can be selected for mixing with thetoner include those particles that are capable of triboelectricallyobtaining a charge of opposite polarity to that of the toner particles.Illustrative examples of suitable carrier particles include granularzircon, granular silicon, glass, steel, nickel, ferrites, iron ferrites,silicon dioxide, and the like. Additionally, there can be selected ascarrier particles nickel berry carriers, comprised of nodular carrierbeads of nickel, characterized by surfaces of reoccurring recesses andprotrusions thereby providing particles with a relatively large externalarea. The carrier particles may be used with or without a coating, thecoating generally being comprised of fluoropolymers, such aspolyvinylidene fluoride resins, terpolymers of styrene, methylmethacrylate, a silane, such as triethoxy silane, tetrafluoroethylenes,other known coatings and the like. The carrier core may be at leastpartially coated with a polymethyl methacrylate (PMMA) polymer. PMMA isan electropositive polymer that will generally impart a negative chargeon the toner by contact. The coating has, in embodiments, a coatingweight of from about 0.1 weight percent to about 5.0 weight percent, orfrom about 0.5 weight percent to about 2.0 weight percent of thecarrier. The carrier particles may be prepared by mixing the carriercore with from about 0.05 weight percent to about 10 weight percent ofpolymer, such as from about 0.05 weight percent to about 3 weightpercent of polymer, based on the weight of the coated carrier particles,until the polymer coating adheres to the carrier core by mechanicalimpaction and/or electrostatic attraction. Various effective suitablemeans can be used to apply the polymer to the surface of the carriercore particles, for example, cascade-roll mixing, tumbling, milling,shaking, electrostatic powder-cloud spraying, fluidized bed,electrostatic disc processing, and with an electrostatic curtain. Themixture of carrier core particles and polymer may then be heated to meltand fuse the polymer to the carrier core particles. The coated carrierparticles are then cooled and classified to a desired particle size.

Carrier particles can be mixed with toner particles in any suitablecombination in embodiments. In some embodiments, for example, about 1 toabout 5 parts by weight of toner particles are mixed with from about 10to about 300 parts by weight of the earner particles.

In embodiments, any known type of image development system may be usedin an image developing device, including, for example, magnetic brushdevelopment, jumping single-component development, hybrid scavengelessdevelopment (HSD), etc. These development systems are well known in theart, and further explanation of the operation of these devices to forman image is thus not necessary herein. The toners are included in ahousing of the device, and provided from the housing to an imagedevelopment station of the device in forming an image. Once the image isformed with toners/developers via a suitable image development methodsuch as any one of the aforementioned methods, the image is thentransferred to an image receiving medium such as paper and the like. Thedevice may include a fuser roll member. Fuser roll members are contactfusing devices that are well known in the art, in which heat andpressure from the roll are used in order to fuse the toner to theimage-receiving medium. Typically, the fuser member may be heated to atemperature just above the fusing temperature of the toner.

The toners described herein are further illustrated in the followingexamples. All parts and percentages are by weight unless otherwiseindicated.

It will be appreciated that various of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Also,various presently unforeseen or unanticipated alternatives,modifications, variations or improvements therein may be subsequentlymade by those skilled in the art, and are also intended to beencompassed by the following claims.

While the description above refers to particular embodiments, it will beunderstood that many modifications may be made without departing fromthe spirit thereof. The accompanying claims are intended to cover suchmodifications as would fall within the true scope and spirit ofembodiments herein.

The presently disclosed embodiments are, therefore, to be considered inall respects as illustrative and not restrictive, the scope ofembodiments being indicated by the appended claims rather than theforegoing description. All changes that come within the meaning of andrange of equivalency of the claims are intended to be embraced therein.

EXAMPLES

The examples set forth herein below and are illustrative of differentcompositions and conditions that can be used in practicing the presentembodiments. All proportions are by weight unless otherwise indicated.It will be apparent, however, that the present embodiments can bepracticed with many types of compositions and can have many differentuses in accordance with the disclosure above and as pointed outhereinafter.

Comparative Example 1 Phase Inversion Emulsion Procedure

100 g of a high molecular weight crystalline polyester resin (High Mwpolyester resin A) was weighed out in a 1 L kettle. The acid value forHigh Mw polyester resin A is 13.22 mg KOH/g resin. 100 g of methyl ethylketone (MEK) and 10 g of iso-propanol (IPA) were weighed out separatelyand mixed together in a beaker. The solvents were poured into a kettle.The kettle, with its cover on, a gasket, a condenser and two rubberstoppers, were placed inside a water bath set at 45° C. (maintained Trat 42-43° C.).

The agitator (anchor blade impeller) was set up in the kettle to rotateat approximately 50 RPM. After 1.5 hours, when all of the resins havedissolved, the bath temperature was decreased to 42° C. (maintained Trat 40° C.) the rotation was adjusted to approximately 100 RPM. After 15minutes, 6.01 g of 10% NH₄OH (calculated by the formula: neutralizationrate×amount of resins in grams×acid number×0.303×10−2) was added to themixture drop-wise with a disposable pipette through a rubber stopperduring a period of 2 minutes. The mixture was left alone for 10 minutes.300 g of de-ionized water (DIW) was then added into the kettle by a pumpthrough a rubber stopper. The first 200 g were added in 90 minutes withthe pump set to a rate of 4.44 g/min. A small sample (i.e., 3-4 drops)was taken with a pipette at 60 minutes. The emulsion sample was dilutedwith hot DIW (40° C.) in a vial for the particle size measurement. Thelast 100 g are added in 30 minutes with the pump set to a rate of 6.7g/min. The apparatus was dismantled, and the mixture was poured into aglass pan, which was kept in the fume hood overnight and stirred by amagnetic stir-bar. A sample was taken before evaporation for a particlesize (diluted with hot DIW and pH test.

The latex particle size was D₅₀=178.5 nm, D₉₀=244.7 nm at 35.2% solidloading.

Comparative Example 2 High Molecular Weight Polyester Resin with AmmoniaHydroxide as Neutralization Agent (Control PIE)

Eight branched high molecular weight polyester resin samples, R1, R2,R3, R4, R5, R6, R7, R8 (R8-1 and R8-2), and one reference sample, HighMw polyester resin A, were attempted to be emulsified using nominal PIEprocess as described in Comparative Example 1, except that instead ofpumping DIW to resin solution with 50 RPM agitation, DIW was added dropwise to the resin solution manually with hand shaking.

The detailed process is described below. 20 grams of resin was chargedin 125 mL plastic bottle and was dissolved with 20 grams MEK and 2 gramsIPA mixture in 50° C. water bath with stirring. 3.24 grams of dissolvedresin was transferred into a 10 mL vial followed by adding 10% NH₄OH tothe vial and hand shaken for 2 minutes for complete mixing. The amountof ammonium hydroxide was estimated based on the neutralization ratioaccording to the following equation: neutralization ratio in anequivalent amount of 10% NH₃/resin(g)/resin acid value/0.303100. About3-4 grams water was then added to the above mixture drop wise withshaking to obtain the emulsion. The emulsification process is consideredto be unsuccessful (even after trying different neutralization ratiosand different solvent ratios, such as, resin:MEK:IPA (20:20:1.5), orresin:MEK:IPA (20:40:4), (1) if the resulting emulsion does not have aparticle size of 100-300 nm, or (2) had produced broad particle sizedistribution or even with bimodal or tri modal peak distribution

The results of this PIE process in emulsifying the branched polyesterresin samples are shown in Table 1. All eight resin samples that weredissolved in ratio of 10:10:1 or 10:10:1.5 (resin:MEK: IPA) failed toproduce stable emulsions, except for the reference sample High Mwpolyester resin A. Only one sample R8-2 achieved good stable latexwithin target particle size (with higher solvent ratio which is 10:20:1of resin: MEK:IPA). The resulting emulsion of samples R3 and R4 containparticles that were too large and the neutralization operating rangeswere very narrow.

TABLE 1 Acid Value Best (mg Soften Particle KOH/g Point Resin/MEK/IPASize Neutralization Resin ID resin) (° C.) ratio (nm) Ratio (%) Note R19.3 122.5 10/10/1.5 None — R2 10.13 124.3 10/10/1.5 None — A3 8.52 125.510/10/1.5 434 65 Narrow emulsify window R4 11.7 124.1 10/10/1.5 477 60.2Narrow emulsify window R5 12.99 — 10/10/1 None — R6 13.6 120.4 10/10/1None — R7 8.4 120.0 10/10/1 None — R8-1 8.1 120.2 10/10/1 None — R8-28.1 120.2 10/20/2 153-188 20-25 High Mw 12.2 118.1 10/10/1 134-200 30-55polyester resin A

Example 3 High Molecular Weight Polyester Resins with Organic Amine asNeutralization Agent (Modified PIE)

Eight branched polyester resin samples, R1, R2, R3, R4, R5, R6, R7, R8(R8-1 and R8-2), and the two reference resin samples were emulsifiedusing the following modified PIE: 20 grams resin was charged in 125 mlplastic bottle and dissolved with 20 grams MEK and 2 grams IPA mixturein 50° C. water bath with stirring. 3.24 grams dissolved resintransferred to a 10 mL vial followed by adding 10% triethylamine to thevial and hand shaken for 2 minutes for complete mixing. The amount oftriethylamine was estimated based on the neutralization ratio. About 3-4grams water was then added to the above mixture drop wise with shakingto obtain the emulsion.

All resins, including the two reference samples were emulsifiedsuccessfully in 10:10:1 ratio (resin:MEK:IPA) and the emulsions obtainedhad particle size of 150-200 nm and the neutralization ratio latitudewas wide which mean the process is easier to scale up. The results ofsuccessfully produced latexes with modified PIE are shown in Table 2.

TABLE 2 Acid Value Soften Resin/ Best Neutral- (mg KOH/g Point MEK/IPAParticle ization Resin ID resin) (° C.) ratio Size (nm) Ratio (%) R1 9.3122.5 10/10/1.5   159.8 122 R2 10.13 124.3 10/10/1.5 201 116 R3 8.52125.5 10/10/1.5 186 105 R4 11.7 124.1 10/10/1.5 256 97 R5 12.99 —10/10/1 142-147  94-102 R7 8.4 120.0 10/10/1 155-190 110-145 R8-1 8.1120.2 10/10/1 164 100 R8-2 8.1 120.2 10/20/2 161-200 201-289 High Mw12.2 118.1 10/10/1 134-200 111 polyester resin A Low Mw 11.3 116.410/10/1 113-179 69.7 polyester resin B

Example 4 High Molecular Weight Polyester Resins with Triethylamine(Larger Scale PIE Latex Used to Make Toner)

Two high molecular weight polyester resins and two reference resins werechosen to make bench scale latex with triethylamine as neutralizationagent.

100 grams resin was charged in 500 ml plastic bottle and was dissolvedwith 100 grams MEK and 10 grams IPA mixture (i.e., resin:MEK:IPAratio=10:10:1) in 45 t water bath with stirring. Triethylamine was addedto plastic bottle and hand shaking 2 minutes for complete mixing. Theamount of triethylamine was estimated based on the neutralization ratioaccording to the following equation: neutralization ratio in anequivalent amount of 10% triethylamine (g)/resin(g)/resin acidvalue/constant (e.g., 1.804)*100. About 125 grams water was then addedto the above mixture drop wise with shaking to obtain the emulsion.

All resins emulsified successfully and the neutralization ratio was thesame as mini PIE experiments and the resulting emulsions obtained hadsimilar particle size as mini PIE experiments. This indicates that theorganic amine neutralization agent had very good repeatability. The dataof successfully bench scale produced latexes with modified PIE is shownin Table 3.

TABLE 3 Acid Value Best Scale (mg Particle (used KOH/g Soften PointResin/MEK/IPA Size Neutralization resin) Resin ID resin) (° C.) ratio(nm) Ratio (%) (g) R7 8.4 110 10/10/1 164.9 132 50 R7 8.1 117 10/10/1144 99 100 High Mw 12.2 102 10/10/1 167 111 200 polyester resin A Low Mw11.3 116.4 10/10/1 176 69.7 76 polyester resin B

Toner particles were prepared from polyester resins Low Mw polyester Band High Mw polyester A emulsified by this modified PIE process thatuses an organic amine such as triethylamine instead of ammoniumhydroxide. The resulting latexes were used to make an emulsionaggregation toner.

Preparation of Emulsion Aggregation Toner:

Into a 2 liter glass reactor equipped with an overhead mixer was added156.35 g low molecular weight amorphous resin1 emulsion (21.35 wt %),108.06 g high molecular weight amorphous resin 2 emulsion (30.89 wt %),29.03 g crystalline resin emulsion (33.51 wt %), 42.57 g IGI waxdispersion (30.34 wt %) and 49.37 g black pigment Nipex 35 (17.00 wt %).Separately 2.51 g Al2(SO4)₃ (27.85 wt %) was added in as flocculentunder homogenization. The mixture was heated to 40.0 C to aggregate theparticles while stirring at rpm 200 rpm. The particle size was monitoredwith a Coulter Counter until the core particles reached a volume averageparticle size of 4.63 μm with a GSD volume of 1.26, GSD number of 1.31,and then a mixture of 91.8 g and 63.45 g of above mentioned resin 1 andresin 2 emulsions were added as shell material, resulting in acore-shell structured particles with an average particle size of 5.71microns, GSD volume 1.20, GSD number 1.23. Thereafter, the pH of thereaction slurry was then increased to 7.8 using 4 wt % NaOH solution tofreeze the toner growth. After freezing, the reaction mixture was heatedto 85° C. while maintaining pH greater than 7.8. Toner particles haveaverage particle size of 6.61 microns, GSD volume 1.26, GSD number 1.33.After being kept at 85° C. for about 30 min, pH was reduced to 7.0stepwise over 44 min using pH 5.7 acetic acid/sodium acetate (HAc/NaAc)buffer solution for coalescence. The toner was quenched aftercoalescence, resulting in a final particle size of 6.21 microns, GSDvolume of 1.26, GSD number of 1.33. The toner slurry was then cooled toroom temperature, separated by sieving (25 μm), filtration, followed bywashing and freeze dried.

The resulting toner particle properties as compared those prepared bythe conventional process are included in Table 4. The particle size andGSDv/n values are within the desired specification range. The particleshape as measured by circularity was also within specifications.

TABLE 4 Conventional Process Inventive Process Raw Materials Resin 1:Low molecular Low molecular weight/ (resin) weight polyester high weightpolyester Information amorphous Resin amorphous Resin Resin 2: highmolecular Emulsified weight polyester withTriethylamine amorphous ResinLatexes Emulsified resin 1 and Emulsified resin 1 and resin 2 withnormal resin 2 with triethylamine PIE process as neutralization agentParticle Size D₅₀/GSDv/GSDn = D₅₀/GSDv/GSDn = 5.71/1.20/1.236.21/1.26/1.33 Circularity 0.952 0.952 Note Control

Two toner samples were blended with additives and tested using Xeroxmethods for charging evaluation. The modified PIE sample is comparedagainst the control sample above.

As can be seen in FIGS. 1 and 2, the parent charging for the modifiedPIE sample looks slightly higher in A-zone and lower in J-zone than thecontrol sample (FIG. 1). With additives, the modified sample hasidentical charging to the control sample (FIG. 2).

The unit Q/d was measured using a charge spectrograph with a 100 V/cmfield, and was measured visually as the midpoint of the toner chargedistribution. The charge was reported in millimeters of displacementfrom the zero line (mm displacement can be converted tofemtocoulombs/micron (fC/μm) by multiplying by 0.092).

The two toner samples were also submitted for fusing evaluation. Theresults demonstrate that (1) cold offset temperature (i.e., Lower limitfuser roll temperature where toner fails to adhere to the substrate andsignificant quantities offset to the fuser roll), (2) crease fix MFT(i.e., minimum fusing temperature required to achieve acceptable toneradhesion to the substrate), and (3) temperature required to reach gloss40 (i.e., fuser roll temperature required so the print gloss is 40 glossunits) were the same for the two samples.

Example 5 High Molecular Weight Polyester Resins

All the polyester resin samples have a molecular weight (Mn) in therange between 86,000 and 121,000 and a Tg onset between 56° C. and 65°C.

The polyester resin samples were produced in two stages. In the firststage ethoxylated BPA (E-BPA), propoxylated BPA (P-BPA), terephthalicaicd (TA), and dodecenylsuccinic anhydride (DDSA) were condensed withcatalyst (Fastcat 4100) at 220° C. under N₂ flow over 6 hours. In thesecond stage, a branching agent trimellitic anhydride (TMA) was addedand the reaction proceeded at 220° C. under N₂ flow over 19 hours. Theend point for the polymerization was monitored by acid value titrationsand viscosity. The target viscosity and acid value are 98±5 poise and12.4±1 mg KOH/g resin, respectively. Once the desired properties wereachieved, the reactor was discharged. The characterization of allpolyester resins are shown in Table 5.

TABLE 5 Av (mg Mw KOH/g (xK) Mn (xK) PD Tg (° C.) resin) Ts (° C.) HighMw 84.08 5.22 16.11 56.4 12.2 118.1 polyester resin A(1001) reference R141.17 5.18 7.95 59.93 9.3 122.5 R2 52.55 4.6 11.43 58.2 10.13 124.9 R356.9 5.1 11.15 60.01 8.5 125.5 R4 59.75 5.69 10.51 60.23 11.7 124.1 R531.64 3.1 10.14 59.79 12.99 \ R6 34.91 5.09 5.86 61.72 13.6 120.4 R741.62 5.5 7.56 57.67 8.4 120 R8 44.12 5.88 7.51 56.78 8.1

Example 6 Preparation of Toners

A toner particle T1 was prepared from high Mw polyester resin A and lowMw polyester resin B emulsified by the modified PIE process of thedisclosure that uses an organic amine such as triethylamine instead ofammonium hydroxide. The resulting latexes were used to prepare anemulsion aggregation toner according to the procedure described above.The resulting toner particle properties are included in Table 6. Theparticle size and GSDv/n values are within the spec range. The particleshape as measured by circularity was also within specification.

TABLE 6 T2 (Control) T1 Raw Low Mw polyester resin B/ Low Mw polyesterresin B/ Material High Mw polyester resin A A56 Information Latex Low Mwpolyester resin B Low Mw polyester resin B ammonium hydroxide latextriethylamine latex High Mw polyester resin A High Mw polyester resin Aammonium hydroxide latex triethylamine latex Latex Size: 167.4 nm/144.3nm Particle 5.71/1.20/1.23 5.71/1.23/1.40 Size (nm) Circularity 0.9520.966 Note Control

The toner sample T1 and the control toner sample Y03 have been examinedusing a Hitachi SU8000 scanning electron microscope.

The toner particles within the sample of T1 were similar in surfacenature to the control toner sample T2, and were also more spherical inshape, i.e., having higher circularity than control toners. All SEMmicrographs are shown in the FIG. 3 and FIG. 4.

The toners sample T1 and the control toner sample Y03 were submitted forfusing evaluation. Fusing performance (gloss, crease, and hot offsetmeasurements) of particles was collected and results are shown below.

T2 (prepared according to control PIE): minimum fixing temperature(MFT)=113, Gloss Mottle=190 (severe mottle), Hot offset=200° C.

Y09 (prepared according to modified PIE): MFT=111, Gloss Mottle 190, Hotoffset=205° C.

The print glosses for the control and modified PIE toners were nearlyidentical up to 165° C. There were some differences at the highertemperatures with T2 showing severe gloss mottle at 190° C. while Y09shows a more gradual drop in gloss as temperature increases.

FIG. 5 shows a graph illustrating the gloss versus fusing temperaturefor T1 and T2

The toner made using resins from the modified PIE process have similaror better fusing performance (e.g., fusing latitude) when compared tothe control PIE process toner.

SUMMARY

In summary, there is provided a modified PIE process using organicamines to successfully emulsify high molecular weight amorphous resinand emulsify high molecular branched amorphous polyester resin toachieve the desired particle size of 100-250 nm. The experimentsconducted demonstrated that large scale latex could be prepared usingthis process and toner particles with the desired particle propertieswere subsequently produced from these latexes.

The claims, as originally presented and as they may be amended,encompass variations, alternatives, modifications, improvements,equivalents, and substantial equivalents of the embodiments andteachings disclosed herein, including those that are presentlyunforeseen or unappreciated, and that, for example, may arise fromapplicants/patentees and others. Unless specifically recited in a claim,steps or components of claims should not be implied or imported from thespecification or any other claims as to any particular order, number,position, size, shape, angle, color, or material.

All the patents and applications referred to herein are herebyspecifically, and totally incorporated herein by reference in theirentirety in the instant specification.

What is claimed is:
 1. A process comprising: mixing at least onepolyester resin comprises a high molecular weight polyester having anumber average molecular weight of from about 86,000 and 121,000 with asolvent to form a resin mixture; neutralizing the resin mixture with aneutralizing agent in water; and agitating the resin mixture andneutralizing agent in water to form an aqueous emulsion, wherein theneutralizing agent is selected from the group consisting oftriethylamine, triethaneolamine, and mixtures thereof; further whereinwherein the solvent comprises two organic solvents and the ratio of thetwo organic solvents is from about 5:1 to about 50:1.
 2. The process ofclaim 1, wherein the polyester amorphous resin comprisespropoxylated-bisphenol-A, ethoxylated-bisphenol-A, and mixtures thereof.3. The process of claim 1, wherein the polyester resin has a low acidvalue of from about 3 mg KOH/g of resin to about 200 mg KOH/g of resin.4. The process of claim 1, wherein the solvent is selected from thegroup consisting of alcohols, esters, ethers, ketones, amines, andmixtures thereof.
 5. The process of claim 1, wherein the aqueousemulsion has a particle size in a range produce emulsions with particlesize in the desired range of from about 100 to about 250 nm.
 6. Theprocess of claim 1, wherein the aqueous emulsion has a narrow particlesize distribution.
 7. The process of claim 1, wherein the resin mixturecomprises a weight ratio of the resin to solvent of about 2:1 to about1:5.
 8. The process of claim 1, wherein the neutralization agent ispresent in the aqueous emulsion in an amount of from about 0.001% toabout 50% percent by weight of the total weight of the resin.
 9. Theprocess of claim 1, wherein the aqueous emulsion is used to form anemulsion aggregate toner.
 10. A process comprising: mixing at least onepolyester resin comprises a high molecular weight polyester having anumber average molecular weight of from about 86,000 and 121,000 with asolvent to form a resin mixture, wherein the polyester resin is a highmolecular weight polyester amorphous resin or a high molecular weightbranched polyester amorphous resin; neutralizing the resin mixture witha neutralizing agent in water; and agitating the resin mixture andneutralizing agent in water to form an aqueous emulsion, wherein theneutralizing agent is an organic amine selected from the groupconsisting of triethylamine, triethaneolamine, and mixtures thereof;further wherein wherein the solvent comprises two organic solvents andthe ratio of the two organic solvents is from about 5:1 to about 50:1.11. The process of claim 10, wherein the aqueous emulsion has a particlesize in a range produce emulsions with particle size in the desiredrange of from about 100 to about 250 nm and has a narrow particle sizedistribution.